Methyl vinyl ether copolymers

ABSTRACT

Methyl vinyl ether is copolymerized with a comonomeric compound of the formula: CH2=CHOR wherein R is phenyl or alkyl of from three to 30 carbon atoms, to give a copolymer containing from 20 to 85 weight percent of said comonomeric compound and having an inherent viscosity (0.1 percent solution in toluene) at 25* C. in the range of 0.6 to 2.0. The resulting copolymer is soluble in hydrocarbon lubricating oils and exhibits a unique combination of properties, such as viscosity index improver, thickener, good shear stability, good 0* F. properties, and as ashless dispersant for gums, resins and other oxidation products, present or formed, in the lubricating oil during the operation of combustion engines of various types.

United States Patent Schultz et a1.

[451 July 11, 1972 [54] METHYL VINYL ETHER COPOLYMERS [72] Inventors: Herman S. Schultz, Easton; William Katzenstein, Broomal; Earl P. Williams, Pen Argl, all of Pa.

Related U.S. Application Data [60] Division of Ser. No. 691,935, Dec. 20, 1967, Pat. No. 3,541,015, which is a continuation-in-part of Ser. No. 515,201, Dec. 20, 1965, abandoned.

[56] References Cited UNITED STATES PATENTS 2,020,703 11/1935 Schumann ..260/9l.l 2,108,994 2/1938 Reppe ..8/6

Vandenberg ..260/91. 1 La! ..260/91.1

Primary Examiner-Joseph L. Schofer Assistant Examiner-C. A. Henderson, Jr.

AttorneySamson B. Leavitt, George L. Tone and Walter C. Kehm [5 7] ABSTRACT Methyl vinyl ether is copolymerized with a comonomeric aome lindpf the female; C 2 O wherein R is phenyl or alkyl of from three to 30 carbon atoms, to give a copolymer containing from 20 to 85 weight percent of said comonomeric compound and having an inherent viscosity (0.1 percent solution in toluene) at 25 C. in the range of 0.6 to 2.0. The resulting copolymer is soluble in hydrocarbon lubricating oils and exhibits a unique combination of properties, such as viscosity index improver, thickener, good shear stability, good 0 F. properties, and as ashless dispersant for gums, resins and other oxidation products, present or formed, in the lubricating oil during the operation of combustion engines of various types.

6 Claims, No Drawings METHYL VINYL ETHER COPOLYMERS This application is a division of application Ser. No. 691,935, filed Dec. 20, 1967, now US. Pat. No. 3,541,015, which is in turn a continuation-in-part of application Ser. No. 515,201, filed Dec. 20, 1965 and now abandoned.

This invention relates to a new and useful class of methyl vinyl ether copolymers and to hydrocarbon lubricating oil compositions containing the same.

The majority of lubricating oil compositions for combustion engines are based on refined lubricating oils modified by specific additives that impart further desirable characteristics, such as high viscosity index, good thickening properties in the useful temperature range, shear stability, detergency and sludge inhibition. In developing lubricating oil additives to impart these characteristics, two or more materials must be added to the base lubricating oil without adversely affecting other desirable performance characteristics of the finished lubricant. It is well-known that multi-functional additives or additive systems that improve two or more properties of the base lubricating oil have been and are the object of extensive research.

Poly (methyl vinyl ether) is insoluble in lower aliphatic hydrocarbons and lube oils. Poly (ethyl vinyl ether) while soluble in heptane, is insoluble in lube oils. Poly (alkyl vinyl ethers), i.e., homopolymers, wherein the alkyl ranges from three to about 18 carbon atoms, while soluble in heptane and lube oils, do not exhibit, when employed as lube oil additives, high viscosity index, satisfactory thickening, dispersancy, good shear stability, etc. 7

It is the principal object of the present invention to provide a new and useful class of copolymers of methyl vinyl ether with one or more other higher alkyl or aryl vinyl ethers which surprisingly exhibit a unique combination of properties in hydrocarbon lubricating oil compositions.

A further object of the present invention is to provide an improved lubricating composition containing a single multifunctional additive which not only acts as viscosity index improver, thickener, but also displays good shear stability, good F. properties, and functions as an ashless dispersant for gums, resins and other oxidation products which may be present or be formed in the lubricating oil during the operation of combustion engines of various types.

Other objects and advantages will become more clearly evident from the following description.

We have discovered that when methyl vinyl ether is copolymerized in certain weight percent proportions with certain weight percent proportions of an arylor alkyl-vinyl ether in which the alkyl contains from three to 30 carbon atoms, a new class of copolymers are obtained which are soluble and which exhibit a unique combination of properties in hydrocarbon lubricating oils. In view of this solubility and unique combination of properties, the copolymers are ideally suited as multi-functional additives to hydrocarbon lubricating oils. When used in lubricating oils in amounts in the concentration range of one to four weight percent, the multi-functional additive copolymers of the present invention impart high viscosity index, satisfactory thickening, excellent dispersancy, good shear stability, and good 0 F. properties. The multi-functional additive copolymers may be added advantageously in the same concentration range to fuel oils or jet fuels to disperse sludge.

The multi-functional additive copolymers can be made up as concentrates in a hydrocarbon lubricating oil stock in the order of 30-40 percent for use as a convenient way of incorporating or dissolving them in a base stock.

A hydrocarbon lubricating oil containing the multi-functional additive copolymers can contain other additives used to improve other properties such as, for example, antioxidants, extreme pressure agents or pour point dispersants, all of which are well-known to the art.

'The multi-functional additive copolymers of the present invention can be employed to improve various hydrocarbon lubricating oils, i.e., base oils of natural origin, such as naphthenic base, paraffin base, mixed base lubricating oils and lubricating oils derived from coal products. The natural hydrocarbon base oils may be blends of different mineral oil distillates and bright stock or blends of such oils with synthetic hydrocarbon lube oils. The oils used generally will have a viscosity in the range of 10-50 SSU (Saybolt Universal Seconds) at 210 F., a viscosity index in the range of 60 to 1 10, a pour point below 0 F., and flash point above 400 F.

The copolymers having the foregoing unique combination of properties are prepared by copolymerizing the following comonomers in the stated weight percent:

Comonomers Methyl Alkyl vinyl ether Wt. vinyl ether Wt. From 3 to 4 alkyl carbon atoms 45-80 20-55 From 8 to 10 alkyl carbon atoms 25-80 20-75 From 16 to 18 alkyl carbon atoms 15-80 20-85 From 20 to 30 alkyl carbon atoms 15-80 20-85 Phenyl vinyl ether 15-80 20-85 The preferred range being in the following weight percent:

Comonomers Methyl Alkyl vinyl ether wt. vinyl ether wt. From 3 to 4 alkyl carbon atoms 55-80 20-45 From 8 to 10 alkyl carbon atoms 30-65 35-70 From 16 to 18 alkyl carbon atoms 40-70 30-60 From 20 to 30 alkyl carbon atoms 15-70 30-85 Phenyl vinyl ether 40-70 30-60 The comonomeric aryland alkyl-vinyl ethers employed with methyl vinyl ether in the aforestated weight percent proportions are characterized by the formula:

CH CHOR wherein R is a straightor branched-chain alkyl of from three to 30 carbon atoms, such as n-propyl, isopropyl, n-butyl, isobutyl, amyl, isoamyl, n-hexyl, 2-ethylbutyl, 1,3-dimethylbutyl, diisopropylmethyl, Z-ethylhexyl, n-octyl, l-methylheptyl, isooctyl, nonyl, n-decyl, l-methyl-4-ethyl-octyl, n-tetradecyl, cetyl, n-octadecyl eicosyl, ceryl and myricyl, or aryl such as phenyl. Vinyl alkyl ethers containing the latter three alkyl groups are prepared by vinylation of eicosyl alcohol and other high boiling alcohols such as ceryl from Chinese wax and myricyl from carnauba wax by acetylene in accordance with the procedure described in'U. S. Pat. No. 2,045,393.

Mixed alkyl vinyl ethers may also be employed as comonomers with the methyl vinyl ether. Such mixed ethers are readily prepared by vinylation of alcohols produced by the 0x0 process from mono-olefinic hydrocarbons of about eight to 22 carbon atoms, or vinylation of mixed alcohols having from six to 22 carbon atoms obtained by the sulfation of aolefins of from six to 22 carbon atoms with sulfuric acid followed by hydrolysis in accordance with known procedures.

In copolymerizing the foregoing comonomers, a boron trifluoride (ethrate) in 1,4-dioxane is employed as a catalyst in heptane toluene as heptane toluene mixtures usually beginning at 0 C. Other boron trifluoride complexes, Friedel- Craft or cationic polymerization catalysts can also be used. Prior to copolymerization, it is desirable that each of the comonomers be purified with respect to organic impurities and water by either sodium treatment, or distillation over sodium followed by storage of sodium ribbon. The dioxane, heptane and toluene should be acid washed, dried, distilled and stored over sodium ribbon. The copolymerization reaction should begin at 0 C. (ice bath in Dewar flask). A temperature as low as C. (dry ice-acetone bath) can be used.

The reactor employed in preparing the copolymers of the present invention was a citrate of magnesia bottle capped with perforated crown cap over a self-sealing butadieneacetylonitrile copolymer rubber (solvent extracted) line. The top of each bottle reactor is equipped with'any suitable device which will make it possible to inject the comonomers, the catalyst and solvent while employing a hypodermic syringe technique and while keeping a flow of nitrogen around it. A units can be convened to centistoke by dividing by 4.6. nitrogen filled dry box may be used,where appropriate,during The copolymers prepared in accordance with the present the manipulation of the reactor. Every effort should be made invention are also useful in many water-insoluble organic to make the reactants, reaction system, and manipulation of liquid-liquid, liquid-solid, or gas-liquid systems which are not the reactor as anhydrous as possible. The copolymerization compatible (not mutually suspended or dispersed) in the reaction may also be carried out in standard four-neck, roundabsence of the copolymer.

bottom,or Morton flasks appropriately equipped to meet the The following examples show how the oil soluble foregoing reaction requirements. The time to complete the copolymeric multi-functional additives are prepared and the copolymerization reaction may range from one-half to unique properties obtained when incorporated in hydrocarhours together with variations, as will be noted in the illustral0 bon lubricating oils. tive working examples.

The copolymers thus obtained will have an inherent viscosi- EXAMPLES l to 6 y I i Percent Solution in 'mlnene of from The following reactions were carried out in carefully about 0.5 to 2.0. Those having an inherent viscosity of 0.6 to deaned dried and Capped citrate f magnesia homes 20, however, are preferred for the purpose of the present inequipped with f t d crown Cap and m i Since y P the desned Fomblnnnon of P acrylonitrile copolymer rubber self-sealing lines. Methyl vinyl nes when added 9 hydrocarbon ether (purified and dried over sodium ribbon) was transferred Th cqpolymenc d t may-be n or orated or diss e hrough a closed initially evacuated system from the storage dlremly a hydrocarbon lnbncahng on with heanng, vessel into the cooled reactor bottle by way of a hypodermic Induced as a toluene solutlonr followed by Shipping in a flash needle. The other reagents were then charged into the reacevaporator under VaFunm wnh heat n lnnodnced as a tors by the use of hypodermic syringe techniques. The y Solunon 9 y PP In a n comonomer vinyl ether in Example 1 and 2 is a distillation evaporator under vacuum with heating. The latter is used in 1lf i f lsoocty] viny| ether made f 0X0 j t l lustrating the present invention while employing mainly a 100 25 coho].

second solvent refined naphthenic oil in the evaluation of the In Examples 3 and 4 it is 2 ethy|heXy] i ether d i E lube on additive p y amples 5 and 6 it is a fraction from the distillation of the vinyl In evaluating the copolymeric multi-functional additives of ether made f Conoco Alf l 810 alcohol containing about the present invention, the kinematic viscoslties at 100 F. and 44 percent alky] Ca and 55 percent alky] Cw viny] ethers' were determined according to ASTM Procedure D Aliquots ofastock solution containing 0.0929 gm. BF -diethyl etherate per cc. [,4 dioxane total solution was finally injected In the followlng Examples 1 to the vlscoslty lhdlces were into the temperature equilibrated bottle in a 0 C. ice-water calculated according to ASTM p D In Exambath and hand mixed immediately. Table 1A summarizes the P 19, ASTM Procednre D 2270 was p y to Calculate reagents used in the examples. The reaction took place imthe viscosity index. mediately after catalyst injection. The reactors were allowed Shear stability of the copolymer containing oils by means of to stand in the ice-water bath for 22 hours. The reactions were a sonic shear test was determined according to Proposed quenched with a small amount of methanolic ammonia, Method of Test for Shear Stability of Polymer-Containing diluted with reaction solvent, the solution filtered through a Oils, Appendix XII, page l,l60, Vol. I, 38 Edition, Oct, sintered glass funnel to remove the catalyst complex, and the 1961, ASTM Committee D-2 on Petroleum Products and solution pumped under vacuum several 'days first at ambient Lubricants. The shear time used is one-half hour. temperature and then at 40-50 C. to remove solvent.

TABLE 1A Weight percent Cc. BF; comonoetherate mer in qlnll Example Gms. (3111s. 00- Ce. Reaction in 1,4- monomer Yield, 0.1% number MVE monomer solvent solvent dioxane mixture percent toluene 13.0 10 18.4 Toluene..- 0.250 53.5 00.5 0.025 14.3 10.3 10.1 lleptanen 0.204 54.0 00.0 0.880 14.1 10.0 18.0 Toluene..- 0.202 54.4 100 0.500 15.1 17.3 20.2 l'lttpftlneu 0.283 54.1 87.0 1.005 10.4 10.0 22.0 Toluene... 0. 300 54.5 100 0.500 10.0 23.2 20.2 He tane 0.300 54 2 80.0 1.08

The sludge dispersancy test is that described in paper Table 1B summarizes the results of testing 2 weight percent pages 307-318 of Section 5 Proceedings of the Fifth World solution of the copolymers in 100 second solvent refined Petroleum Congress, 1959, New York, by R. M. Jolie. All of 55 naphthenic Oil! TABLE 1B Before shear After shear KV21() F./ KV-0 F. in KVIOO F. Example KV F. centistokcs Dispcr- VI/VI percent vise. Number eontistokes VI extrapolated StIIICy decrease (lttl'ttlSt.

1132/4007 143 1,400 Pass /7 7. all/41.00 144 1,200 ...do. /0 17.0 5. 75/32. 8 130 0. 0 8. 07/450 142 1,300 Pass 135/7 10.0 .1 5. 75/32. 74 127 0 7. 70/43. 47 1,200 lass- 130/4 11.0 Acryloid066" 7. 44/37. 22 850 do 127/23 28.5 Base oil 4. 02/22. 03 80 1 (Robin & Haas). the copolymers that tested satisfactorily gave opaque suspen- I i to b noted h h copolymers f E l 3 d 5 510m of dlsperswns, hence all assed" the dlspersancy test as 70 which have an inherent viscosity of0.5, are deficient in V. l. as illustrated hereinafter in Table 1B. compared with related copolymers of Examples 4 and 6. It is Extrapolated oil viscosities. the fi i l pr r generally to be further noted that the shear stability of the commercially used in the trade, were determined according to the method available lube oil additive Acryloid 966 is significantly described on pages 275-276 ofthe 1961 SAE Handbook. poorer than the copolymers of Examples 2, 3, 4 and 6 as it is to be noted that Saybolt Universal seconds viscosity 75 shown by the KV-l00F.% viscosity decrease.

EXAMPLE 7 TABLE 2 KV-2l0" F KV-If' F. in Example KV100 F. centistokes Number eentlstokes VI extrapolated Dlspersancy 7. 98/44. 23 144 1, 600 Pass. 7. 61/42. 41 140 1, 250 Do.

EXAMPLES 9, l0 and 11 The copolymerizations were carried out in the same fashion as in Examples 1 to 6. The comonomer was 2-ethyl hexyl vinyl ether. The reaction solvent was volume percent toluene in heptane. The BF -diethyl etherate in 1,4-dioxane titer was 0.995 g./cc. The reaction bottles were equilibrated with a 0 C. ice-water bath before catalyst injection. Table 3A summarizes the reagents in the examples. The reactions were carried out overnight in a 0 C. bath followed by a usual workup. Table 3B summarizes testing data in the standard 100 second solvent refined stock.

TABLE 3A Cr. BF Weight.

diethyl percent. etherate oomenon lllll Example (lms. Gms. Ce. in 1,4- titer in Yield. 0.1% o. MVE 2-E l IVE solvent. dioxane mixture percent toluene .l l0. 7 7. (i 14. 7 0.1137 11. 5 15.11 0. 57 10 l0. 7 11.11 lti. 5 0.178 '18 114.8 0. (ill 11 8. 0 .l. 2 l3. 8 11.1 11 53. 5 .I5. 3 0. till cooled reactor. 65.4 grams purified and dried isooctyl vinyl EXAMPLE ether (same as used in Examples 1 and 2) were then injected, followed by 78 cc. purified and dried heptane. The reaction mixture was equilibrated with a 0 C. ice-water bath. 0.946 cc. solution of BF -etherate in 1,4 dioxane (0.102 g./cc. titer) was injected to the rapidly stirring solution. Temperature rose quickly to 181 C. in a few minutes and slowly fell back to 6 C. in 18 minutes. The reaction was allowed to proceed overnight at mainly 02C. The next day the viscous reaction mixture was warmed to 40 C. and then quenched with methanol ic ammonia. The yield after workup was 90.6% and ninh (0.1

percent, toluene) is 0.94. Table 2 summarizes testing in the same lube oil stock as Example No. 1 at 2 weight percent concentration.

This copolymerization was carried out in the same fashion as Example 1 except that cetyl vinyl ether was used as comonomer with methyl vinyl ether. 1 1.5 grams methyl vinyl ether, 14.5 grams cetyl vinyl ether and 20.8 cc. of a 50/50 volume percent mixture of toluene and heptane were charged into the reaction bottle. After equilibration with an ice-water bath, 0.181 cc. of a BF -diethyl etherate in 1,4-dioxane solution (0.0995 gm./cc. titer) was injected. lmm'ediate reaction took place and after overnight reaction and workup resulted in a 97.1 percent yield and ninh (0.1 percent, toluene) of 0.70. The weight percent cetyl vinyl ether in the starting mixture is 55.8 percent. Table 4 summarizes the lube oil test data in the standard 100 second solvent refined stock.

TABLE 3B After shear Before shear KV-100 F. 00110., KV-O F. in percent Example weight KV210 F./ centistokes vise. Nnmber percent KV-100 F. VI extrapolated Dispersancy decrease TABLE 4 KV100 F- KV-210 F. KV-0 F. in percent visc- Couc. KV-100 F. VI Disoentistokes decrease after Example percent centistokes persancy extrap. shear 1 5. 53/30. 32 121 1, 050 7. 4 2 7. 01/30. 80 l37/pass 1, 200 11, 0 3 9. 11/52. 31 142 2,000 9.1)

EXAMPLE 8 EXAMPLE l3 A stirred run was carried out as in Example 7. 65 grams methyl vinyl ether were charged as before. 75.4 grams of an isooctyl vinyl ether fraction were charged followed by 98 cc. heptane. 1.15 cc. BF -diethyl etherate in 1,4-dioxane (titer is 0.0995 g. BF -diethyl etherate/cc. solution) were charged into the rapidly stirring 0 C. solution. Temperature rose immediately to 22 C. Temperature was quickly brought back to below 5 C. A second charge of catalyst of the same size as before was added after 3 hours and minutes. The reaction ran overnight and was worked up the same way as before. The yield was 92 percent and ninh (0.1 The lube oil test data is in Table 2.

This polymerization was carried out in the same fashion as Example 1 except that isobutyl vinyl ether was used as comonomer with methyl vinyl ether. 16.8 grams methyl vinyl ether, 26.4 grams isobutyl vinyl ether and 43.2 cc. heptane were charged into the reaction bottle. After equilibration with an ice-water bath, 0.315 cc. BF -diethyl etherate in 1,4-dioxane (titer= 0.0985 gm./cc.) was injected. Immediate reaction took place and after overnight reaction and workup resulted in a 95.8 percent yield and an ninh (0.1 percent, toluene) of 0.81. The weight percent isobutyl vinyl ether in the starting percent toluene)-0.83. mixture is 61 percent. Table 5 summarizes the test data in the standard second solvent refined stock.

TABLE KV-100 F. KV210F./ KV-0 F. percent vise. Example Cone KV 100 F. centistokes Disperdecrease after Number percent centlstokes VI extrap. sancy slnuu', percent 1 5. 32/20. 7 124 1,000 4. 4 2 7. /40. 1 138 1, 200 Pass 3 9. 70/ 54. 4 144 1, S00

EXAMPLE 14 From Table 78 it is clearly evident that the shear stability of This polymerization was carried out in a fashion similar to Example 7. 55 grams methyl vinyl ether were charged into the Morton flask as before. 16.8 cc. toluene and 67.2 cc. heptane were then charged into the reactor followed by 49.8 grams 2- ethylhexyl vinyl ether. 0.915 cc. BF -diethyI etherate in 1,4- dioxane (0.0988 g. BF -etherate in 1 cc. solution) was charged into the rapidly stirring 0 C. solution. The reaction took place immediately. The reaction was allowed to run overnight. After the usual workup the yield was found to be 91.5 percent and ninh (0.1 percent in toluene) is 1.24. Table 6 summarizes the lube oil test data. Lube oil A is a 100 second solvent refined naphthenic stock, Lube oil B is a 10w 30 high wax content oil, and Lube oil C is paraffinic base oil. The concentration is 2 percent.

the alkyl vinyl ether homopolymers, wherein the alkyl is from 3 to 16 carbon atoms, is significantly poorer when compared with the good stability of the copolymers of the present invention as shown in Tables 1B, 3B, 4, 5 and 6. Although the homopolymers show good low temperature properties, they do not show dispersancy.

EXAMPLE 19 This polymerization was carried out in a fashion similar to Example 7 except that a five neck appropriately equipped resin pot was used and the catalyst was added in two increments. 1300 cc. purified anhydrous toluene was added to the reactor by use of a special transfer vessel. The reactor was cooled to 0 C. and 508 grams purified dried 2-ethyl hexyl TABLE 6 Percent KV-l00 F. V1 Cone. KV-210 F./ KV-0 F. percent vise. decrease Lube of KV*100 F. VI eentidecrease after oil polymer eentidispersstokes alter sonic shear, stocks percent stokes aney ext-rep. shear, percent percent A 030/5115 145/pnss 1, 300 11. 0 0. 7 A.. 0 4. 23/24. 05 80 ll. 10. 33/5818 lb l/pnss 1,750 11 ll. 0 5.08/301 l .3 11. 72/77. 48 l35/pztss 3, 000 10.0 0 5.78/1107 EXAMPLES 15 to 18 (Comparative) vinyl ether was added in a similar fashion. The 603 grams pu- The homopolymerization of isobutyl, isooctyl and cetyl vinyl ethers was carried out as in Example 1. The purpose is to show the difference between homopolymers and the copolymers of the present invention. Table 7A shows the homopolymers prepared and their inherent viscosity in toluene.

Table 7B summarizes the lube oil test data of Examples 15 to 18 in the standard 100 second solvent refined stock.

rified dried methyl vinyl ether was added as a liquid by the use of a special transfer cylinder to the reactor at 0 C. 1.30 cc. BF -diethyl etherate in 1,4-dioxane (titer is 0.2 g./cc.BF diethyl etherate in 1,4-dioxane) was charged into the rapidly stirring 0 C. solution. The temperature rose to 24 C. in 25 minutes and fell slowly to 10 C. in another hour. After a total of three hours, 2 cc. more catalyst solution was injected and temperature rose to 13 C. in 15 minutes. After a total of 22 hours with the final temperature at 4 C. the reaction was quenched with methanolic ammonia and worked up as before. The yield was percent and ninh (0.1 percent, toluene) is 1.0.

The resulting polymer was evaluated with 2 commercially available lube oil additives in engine tests as shown in Table 8. The viscosity index values in this table were determined by ASTM procedure D 2270. A viscosity index value while employing ASTM procedure D 567-53 is also given in the accompanying table for comparison.

From Table 8 it is clearly evident that the polymer of Example 19 is not only more shear stable, but actually improves in V. 1. performance while the 2 commercial products lose performance on shearing.

TABLE 8 Polymer Rohm & Haas of Acryloid "Acryloid Ex. 19 763 622" Viscosity at 210F., centistokes (I) 10.48 10.77 10.50 Viscosity at 100F. 61 .1 60.4 55.7 Concentration, Vol. 5.75 5.90 6.30 (33.1 wt.% in oil for Ex. 19) Viscosity index, new soln. before testing (142 by ASTM D 567-53 for Ex. 19) 173 177 204 Viscosity index, after testing in dynamometer engine 178 165 184 Viscosity at F., centistokes 2090 1810 1784 Shear Losses: KV210F.

Viscosity Decrease: Car, high mileage (2) 12.9 17.1 20.1 Car, low mileage (3) 12.8 16.0 19.5 Dynamometer engine (3) 14.1 20.8 21.7 Shear Losses: KV0F. %Viscosity Decrease: Car, high mileage (2) 6.2 17 Dynamometer engine (4) 7.1 7.9 24.6

(1) Base oil viscosity at 210F. 5.54 centistokes 100F. =3S.7 centistokes (2) 1963 Ford Galaxie 289 CID V-8, 60,000 engine miles, 500 miJtest.

(3) 1966 Buick Le Sabre 340 CID V-S, 10,000 engine "500 miJtest. (4) 1960 Olds Seq. 1 Engine, 2500 rpm. no load,5 hrs/test.

Viscosity: SUS/100F. 136,000

SUS/210F. 5,350

Acryloid 763 a clear, viscous concentrate of methacrylic polymer in Mid-Continent solvent-refined 150 SUS/ 100 F. neutral oil.

Viscosity: sus/ 100 1 7,200 SUS/210F. s00

Acryloid 966"-a hazy, viscous polymer concentrate in solvent-refined 100 SUS/ 1 00F. neutral oil.

Viscosity: SUS/l00F.

We claim:

1. Oil soluble copolymer of methyl vinyl ether and a com pound having the formula CH CHOR wherein R is selected from the group consisting of phenyl and an alkyl of from three to 30 carbon atoms, said copolymer containing from 20 to weight percent of a compound having the said formula, said copolymer having an inherent viscosity (0.1 percent solution in toluene) at 25 C. in the range of0.6 to 2.0.

2. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 45 weight percent of methyl vinyl ether and 55 weight percent of isooctyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25 C. of

3. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 50 weight percent of methyl vinyl ether and 50 weight percent of 2-ethyl-hexyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25 C. of 1.24.

4. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 40 weight percent of methyl vinyl ether and 60 weight percent of cetyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25 C. of 0 7 5. Oil soluble copolymer according to claim 1 wherein said I copolymer consists of 40 weight percent of methyl vinyl ether and 60 weight percent of isobutyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25 C. of 0.8.

6. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 45 weight percent of methyl vinyl ether and 55 weight percent of decyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25 C. of 

2. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 45 weight percent of methyl vinyl ether and 55 weight percent of isooctyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25* C. of 0.9.
 3. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 50 weight percent of methyl vinyl ether and 50 weight percent of 2-ethyl-hexyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25* C. of 1.24.
 4. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 40 weight percent of methyl vinyl ether and 60 weight percent of cetyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25* C. of 0.7.
 5. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 40 weight percent of methyl vinyl ether and 60 weight percent of isobutyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25* C. of 0.8.
 6. Oil soluble copolymer according to claim 1 wherein said copolymer consists of 45 weight percent of methyl vinyl ether and 55 weight percent of decyl vinyl ether and having an inherent viscosity (0.1 percent solution in toluene) at 25* C. of 1.2. 